Atmospheric oxygen element with regenerating manganese chloride solution as electrolyte

ABSTRACT

An atmospheric oxygen element with a cathode of activated charcoal and carbon black. A manganese chloride solution is used as electrolyte. The anode consists of zinc sheets. The capacity of this element depends on the amount of MnCl 2 . This amount can be increased by adding manganomanganite (MN 2  O3) produced by precipitation with an alkaline solution in the presence of oxygen. During the delivery of current, ZnCl 2  is created, which replaces the bivalent manganese in the manganite with zinc ions and thus dissolves MnCl 2 .

BACKGROUND OF THE INVENTION

An atmospheric oxygen element is described in U.S. Pat. No. 4,442,183, the disclosure of which is hereby incorporated by reference. The atmospheric oxygen element described contains cathode plates, the active part of which comprise a mixture of activated charcoal and carbon black with a manganese (II) chloride solution as electrolyte. During discharge of the cell the zinc dissolves into ZnCl₂ and manganese chloride is transformed into Mn(OH)₂ at the cathode. Because of the oxygen contained in the atmospheric oxygen elements, the Mn(OH)₂ is oxidized into manganic acid and precipitates at the cathode as Mn₂ O₃. The Mn₂ O₃ reacts with the ZnCl₂, which increases during current delivery, in accordance with the formula:

    Mn.sub.2 O.sub.3 +ZnCl.sub.2 →ZnMnO.sub.3 +MnCl.sub.2

and since the MnCl₂ which has been created continues to react at the cathode, the total formula of current generation in an atmospheric oxygen element with a manganese chloride solution as electrolyte can be written as follows:

    2Zn+3/2O.sub.2 +MnCl.sub.2 →ZnMnO.sub.3 +ZnCl.sub.2

With this reaction it is of particular technical interest that it is possible to react 4 equivalents of zinc to generate current with 1 mol MnCl₂.

Oxygen is available in unlimited amounts, and the amount of zinc required is easily attainable by the choice of the thickness of the anode. However, the amount of MnCl₂ is tied to the amount of electrolyte which can be accommodated in the cell. Solid MnCl₂ ·4(H₂ O) cannot be added to the solution in excess, since it dissolves in moist air and would cause swelling of the cells.

It is therefore an object of the present invention to provide a practical process for generating MnCl₂ in the electrolyte of an atmospheric oxygen element as needed.

It is also an object to provide an atmospheric oxygen element with a source of generating MnCl₂ in the electrolyte.

SUMMARY OF THE INVENTION

In accordance with the above objects, there has been provided a process for generating MnCl₂ in the electrolyte of the cathode of an atmospheric oxygen element comprising the following steps. First, a manganese (II) salt solution is precipitated by adding one equivalent of hydroxide for every equivalent of Mn++ in the presence of oxygen, whereby Mn₂ O₃ is produced. Second, the insoluble Mn₂ O₃ is added to the electrolyte of the cathode. Third, the ZnCl₂ concentration is enriched in the cell during current flow. Fourth, the added Mn₂ O₃ reacts with the ZnCl₂ to produce ZnMnO₃ and MnCl₂. The desired MnCl₂ in the element is thereby generated.

Also in accordance with the above objects, a second embodiment provides a process for generating MnCl₂ in the electrolyte of the cathode of an atmospheric oxygen element comprising the following steps. First, Mn(OH)₂ is precipitated from a manganese (II) salt solution by the addition of alkali in the absence of oxygen. Second, the Mn(OH)₂ of the first step is purified. Third, the purified Mn(OH)₂ of the second step is added to the electrolyte of the cathode, whereby Mn₂ O₃ is formed by oxygen uptake during mixing of the depolorization mass. Fourth, the ZnCl₂ concentration is enriched during current flow in the cell. Fifth, the Mn₂ O₃ formed reacts with the ZnCl₂ to produce ZnMnO₃ and MnCl₂. The desired MnCl₂ in the elements is thereby generated.

Preferably, the third step of the second embodiment further comprises adding moist Mn(OH)₂ to the electrolyte, and further comprises the step, before the fourth step, of saturating the water added with the Mn(OH)₂ by the addition of MnCl₂ ·4H₂ O.

The present invention also preferably provides an atmospheric oxygen element comprising: a zinc anode; a cathode having an aqueous MnCl₂ electrolyte; and a non-soluble Mn₂ O₃ material in the electrolyte for producing MnCl₂ in the electrolyte when current is produced in the element.

BRIEF DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with the invention an insoluble material is therefore added, which only gives off MnCl₂ by the formation of ZnCl₂ during current delivery. Manganomanganite (Mn₂ O₃) is proposed as such, preferably as formed during precipitation from a manganese salt solution with an equivalent amount of an alkaline solution in the presence of oxygen. This product can be added to the electrolyte of the cathode in the form of a dry or wet powder.

Another way of proceeding is to precipitate Mn(OH)₂ from the manganese salt solution with an alkaline solution in the absence of air. The substance purified by the alkaline salt is added, preferably wet, to the cathode mixture. The formation of manganite (Mn₂ O₃) occurs during the mixing process with the addition of oxygen. The water introduced into the mixture by the above reaction and along with the precipitated Mn(OH)₂ is saturated with salt by a corresponding addition of MnCl₂ ·4(H₂ O).

However, the manganite produced does not have to be in electronically conducting contact with the cathode. If the design of the cell permits it, it can also be provided at another place in the electrolyte.

The following examples illustrate how the cathode mixture of the present invention is produced.

Example I: Mixture with the addition of dry Mn₂ O₃

(a) 5 kg carbon black, 5 kg activated charcoal, 5 kg powdered Mn₂ O₃ and 15 kg of a saturated MnCl₂ solution are placed in a mixing drum and mixed until a loose powder mixture is obtained.

(b) If the Mn₂ O₃ is added moist, that is, without having been dried, the water content is determined and 2 kg MnCl₂ ·4H₂ O is added for every kg of water present. 3 kg saturated Managanese chloride solution is thereby produced.

If, for example, the added Mn₂ O₃ contains 2 kg water for every five kg of dry material, the same mixture as in I(a), above, is obtained with the following components: 5 kg carbon black, 5 kg activated charcoal, 7 kg moist Mn₂ O₃, 4 kg MnCl₂ ·4H₂ O, and 9 kg saturated MnCl₂ solution.

Example II: A mixture having the same composition as Example I after oxidation by atmospheric oxygen.

The moisture content of the Mn(OH)₂ is 2 kg water per 5 kg Mn(OH)₂ If Mn(OH)₂ is used, then 5.6 kg of the dry product must be used; this results in 7.84 kg moist Mn(OH)₂ with 2.24 kg water. As a result of oxidizing 5.6 kg Mn(OH)₂ to 5 kg Mn₂ O₃, 1.13 kg of water is formed so that the water content becomes 3.37 kg (i.e., 2.24+1.13=3.37). One must therefor add 6.74 kg of solid MnCl₂ ·4H₂ O, and 10.11 kg saturated Manganese chloride solution results.

The composition of the mixture is therefore as follows: 5 kg carbon black, 7.84 kg moist Mn(OH)₂, 6.74 kg MnCl₂ ·4H₂ O, and 8.26 kg of saturated MnCl₂ solution.

Although specific embodiments are described it will be apparent to one of ordinary skill in the art that modifications can be made within the scope of the present invention which is determined by the appended claims. 

What is claimed is:
 1. A process for generating MnCl₂ in the electrolyte of the cathode of an atmospheric oxygen element having an aqueous MnCl₂ electrolyte and a Zn electrode, comprising the steps of:(a) precipitating a manganese (II) salt solution by adding one equivalent of hydroxide for every equivalent of Mn++ in the presence of oxygen, whereby water insoluble Mn₂ O₃ is produced; (b) adding said water insoluble Mn₂ O₃ to the electrolyte of the cathode; (c) producing current through said element whereby ZnCl₂ is produced in said electrolyte; and (d) reacting said ZnCl₂ with the Mn₂ O₃ added in (b), whereby ZnMnO₃ and MnCl₂ are produced and whereby the desire MnCl₂ is generated.
 2. A process for generating MnCl₂ in the electrolyte of the cathode of an atmospheric oxygen element having an aqueous MnCl₂ electrolyte and a Zn electrode, comprising the steps of:(a) precipitating Mn(OH)₂ from a manganese (II) salt solution by the addition of alkali in the absence of oxygen; (b) purifying the Mn(OH)₂ of step (a); (c) adding the purified Mn(OH)₂ of step (b) to the electrolyte aqueous of the cathode, whereby Mn₂ O₃ is formed by oxygen uptake during mixing of the depolorization mass; (d) producing current through said element whereby ZnCl₂ is produced in said electrolyte aqueous. (e) reacting said ZnCl₂ with the Mn₂ O₃ produced in (c), whereby ZnMnO₃ and MnCl₂ are produced and whereby the desired MnCl₂ is generated.
 3. A process according to claim 2, wherein step (c) further comprises adding moistened Mn(OH)₂ with water to said electrolyte aqueous, and further comprising the step, before step (d) of saturating the water added with the Mn(OH)₂ by the addition of MnCl₂ ·4H₂ O.
 4. An atmospheric oxygen element, comprising:a zinc anode; a cathode having an aqueous MnCl₂ electrolyte; and a non-soluble Mn₂ O₃ material in said electrolyte for producing MnCl₂ in said electrolyte when current is produced in said element.
 5. An element according to claim 4, wherein Mn(OH)₂ is added to said MnCl₂ electrolyte and said Mn₂ O₃ material is produced by oxygen uptake during said addition. 